Photosensitive silver halide composition

ABSTRACT

A photosensitive silver halide composition is disclosed. The composition comprises a silver halide deposited or sorbed on colloidal particles of a hydrous oxide of an element selected from the group consisting of Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg, Al, In, Si, Ge, Sn, Th and mixtures thereof.

Elite States ate t [191 Kenney Dec. 17, 1974 1 PI-IOTOSENSITIVE SILVERHALIDE COMPOSITION [75} Inventor:

I73] Assigncc: Western Electric Company,

' Incorporated, New York, N.Y.

22 Filed: Sept. 19, 1973 [21 Appl. No.: 398,719

John Thomas Kenney, Trenton, NJ.

[52] US. Cl 96/94 BF, 96/108, 96/109,

. 252/213 R [51] Int. Cl G036 1/02 [58] Field of Search 96/94 BF, 95,108, 109,

[56] References Cited UNITED STATES PATENTS 1,995,444 3/1935 Berry eta1. 96/95 2,839,405 6/1958 Jones 96/107 2,950,972 8/1960 Mueller et a1.96/108 3,556,797 1/1971 Pattijw et a1 96/109 3,657,003 4/1972 Kenney117/120 3,767,590 10/1973 Kenney 252 313 R Primary Examiner-Norman G.Torchin Assistant Examiner-Alfonso T. Suro Pico Attorney, Agent, orFirm-J. Rosenstock [57] ABSTRACT 12 Claims, N0 Drawings PHOTOSENSITIVESILVER HALIDE COMPOSITION BACKGROUND OF THE INVENTION 1. Field of theInvention This invention relates to a photosensitive silver halidecomposition and a method of forming the composition and moreparticularly, to a composition comprising a silver halide deposited onsuitable colloidal particles of a hydrous oxide.

2. 1 Description of the Prior Art Silver halide films for photographyare made from silver halide dispersed in gelatin. The resultant gelatinfilms are dimensionally unstable due to both thermal expansion and waterabsorption. Where the silver halide is to be applied to a hydrophobicsurface, the use of gelatin films thereof have not proved satisfactorydue to the poor wettability attained. A gelatin-free silver halide filmwhich is dimensionally stable, which is resistant to decomposition forrelatively long periods of time and which is capable of wettinghydrophobic surfaces is desired and is an object of the subjectinvention.

SUMMARY OF THE INVENTION This invention relates to a photosensitivesilver halide composition and a method of forming the composition andmore particularly, to a composition comprising a silver halide depositedon suitable colloidal particles of a hydrous oxide.

The photosensitive silver halide composition is a wetting silver halidecomposition in that it is capable of l) rendering a non-wettable surfacewettable and (2) tenaciously adhering to the non-w'ettable orhydrophobic surface. The composition comprises a silver halide depositedor sorbed on colloidal particles of a hydrous oxide of at least oneelement selected from the group comprising Be, Mg, Ti, Zr, V, Cr, Mo, W,Mn, Fe, Co, Cu, Zn, Cd, Hg, Al, In, Si, Ge, Sn, Th. The method offorming such a composition includes combining a suitable silver salt,e.g., AgNO with a suitable stable aqueous wetting colloidal solution,formed by a controlled hydrolysis and nucleation reaction, comprising ahalide ion and insoluble hydrous oxide particles of a selected elementin its most stable oxidation state which does not oxidize in water inthe presence of oxygen or reduce silver ions (Be Mg, Ti, Zr, V, V, Cr,MO+6, w-t-fi w u F -HS n +2 +2 +2 va +3 +1 "n+1 n n s -l-i and Th). Theparticles have a size within the range of A to 10,000A and thehydrolysis reaction includes at least l dissolution of a salt of theselected element in an aqueous medium and (2) maintenance of thepH ofthe aqueous medium at a point where no flocculate results.

DETAILED DESCRIPTION The present invention is described primarily interms of a wetting photosensitive silver halide composition and a methodof forming such a composition. However, it will be understood that suchdescription is exemplary only and is for purposes of exposition and notfor purposes of limitation. It will be readily appreciated that theinventive concept described is equally applicable to wettingcompositions comprising a photosensitive halide of an element other thansilver, e.g., Hg.

A suitable silver salt is selected. A suitable silver salt is one whichis water soluble and which is compatible with a suitable colloidalwetting solution, comprising a halide ion and an insoluble hydrous oxideof a selected element, with which the silver salt is destined to becombined. By compatible is meant that the silver salt is not reduced tometallic silver by the colloidal solution and the colloidal state of thesolution is not destroyed by the addition of the silver salt thereto.The silver salt, e.g., AgNO is dissolved in water to form an aqueoussolution typically in concentration of about 0.1-1.0 weight percent ofAgNO It is to be noted, however, that the concentration of the aqueousAgNO solution is not critical and the invention is not to be restrictedthereby.

A suitable aqueous colloidal wetting solution comprising a halide ionand insoluble colloidal particles of a hydrous oxide is selected. Asuitable colloidal wetting solution is a stable colloidal wettingsolution formed by a controlled hydrolysis and nucleation reaction in anaqueous medium wherein (l) colloidal particles of the colloidal solutionhave a size within the range of 10A to 10,000A, (2) colloidal particlesof the colloidal solution comprise an insoluble hydrous oxide of one ormore elements selected from the group comprising Be, Mg, Ti, Zr, V, Cr,Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg, Al, In, Tl, Si, Ge, Sn, Bi, ndTh, (3) no species is present, atomic or ionic, including any species ofthe above enumerated element, which is capable of reducing the silversalt, destined to be added thereto or combined therewith, to metallicsilver, and (4) a halid ion is present. It is to be emphasized that thehydrous oxide is of an element in its most stable oxidation state whichdoes not oxidize in water in the presence of oxygen or reduce silverions to metallic silver. Typical of such elemental oxidation states areBe, Mg, Ti, Zr, V, V+4 3 w m n w s-2 +2 and/or hydroxides:

1. True Hydrous Oxides-Those oxides which include an indefinite amountof H 0 in other than stochiometric fashion. That is, a salt of aselected element hydrous H O.

2. True Hydroxides Those compounds of a salt which contain actualOH-groups. That is, a salt of a selected element only sufficientstochiometric H O to form a hydroxide.

3. Hydrous Hydroxides True hydroxides which also contain hydrOu'sI-I Oin indefinite amounts. That is, a salt of a selected elementstochiometric H O necessary to form a hydroxide hydrous H 0.

4. Hydrous hydrates A salt of a, selected element some of thestochiometric H O necessary to form a hydroxide hydrous H O.

A more detailed explanation of the term hydrous oxide" is contained inboth Inorganic Colloid Chemistry by H. B. Weiser, Vol. 11, The HydrousOxides and I-Iyroxides," Chapter I, John Wiley and Sons, Inc., New York(1935); and Inorganic Chemistry, An Advanced to water carried by thecompound in other than stochiometric fashion. Specifically, such wateris probably 'not carried in chemical fashion but is rather surfacesorbed, occluded or held as a part of the unit crystal.

The hydrolysis reaction includes dissolving a salt of the selectedelement in the aqueous medium and maintaining the pH of the aqueousmedium at a point where no flocculate results.

Suitable colloidal solutions include some of the colloidal wettingsolutions revealed in U.S. Pat. No. 3,657,003, filed Feb. 2, 1970,assigned to the assignee hereof and incorporated by reference herein.More specifically, the following solutions disclosed in U.S. Pat. No.3,657,003 are some suitable colloidal wetting solutions for purposes ofthis invention:

1. The colorless (light, milky white) colloidal wetting solution ofExample l-A which is obtained by (a) dissolving xweight percent ofberyllium chloride [BeCl in 100 ml. of deionized water and (b) raisingthe initial pH of 3.0 to a value of 5.6-5.8 by adding dilute NH OH (H Odilution of 1/20) thereto; 1

2. The colorless (light, milky white) wetting solution of Example l-Bwhich is obtained by (a) dissolving 1 weight percent of berylliumchloride [BeCl in 100 ml. of deionized water and (b) raising the initalpH with NaOH to about 5;

3. The colorless (light, milky white) wetting solution of Example l-Cwhich is obtained by (a) adding V4 to weight percent of berylliumchloride [BeCl 4 to to 100 ml. of deionized water and (b) heating theresultant solution for about 1 hour at 70C;

4. The colorless (light, milky white) wetting solution of Example ll-Awhich is obtained by (a) dissolving 1 weight percent of magnesiumchloride [MgCl or MgCl .6H O] in 100 ml. of deionized water and (b)raising the initial pH with univalent alkali to about 8;

5. The yellowwetting solution of Example llI-C which is obtained by (a)adding particulated titanium metal (Ti) to a hot or boiling (about 80C)concentrated univalent acid, such as HCl, until 0.2-3 weight percent ofthe titanium is dissolved, (b) allowing the solution to cool to roomtemperature, (c) adding sufficient H 0 to quantitatively render all thedissolved titanium (Ti to Ti and (d) raising the pH with a univalentalkali, such as NaOH,- to the range of about 1.2-2.0; 1

6. The blue wetting solution of Example Ill-D which is obtained by (a)adding particulated anhydrous titanium trichloride lTiCl to aconcentrated univalent acid diluted with deionized water 1 weightpercent of the titanium trichloride is dissolved and (b) raising theinitial pH to about 10 with a univalent alkali, such as NaOH, to formTiO 7. The murky, pale yellow wetting solution of example lll-E whichis'obtained by (a) adding one gram of fused titanium metal [Ti] to 70ml. of concentrated HCl, (b) boiling the resultant solution until itassumes a pale blue color. (c) heating the solution without boilinguntil most or all of the titanium metal has been dissolved and reactedto obtain a blue-purple solution having a very low pH. ((1) raising thepH to about 0.5 with lN-NaOH to obtain a pale lavender solution, (e)

adding dilute 50% H 0 to the solution to render it colorless (adding l-2drops in excess), and (f) raising the pH to about 1.0-1.2 with lN-NaOH;

8. The wetting solution of Example III-F which is obtained by adding0.1-5 weight percent of solid particulated (about 100A) titanium dioxide[TiO to water;

9. The wetting solution of Example lll-G which is obtained by (a) adding0.5-5 weight percent of titanium tetrachloride [TiCl to concentrated HCland (b) slowly raising the initial pH of the resultant solution by theaddition thereto of H 0 or a dilute base-such as NaOH or NH OH to a pHof 0.5-5;

10. The colorless (light, milky white) wetting solution of Example IVwhich is obtained by (a) dissolving 1 Weight percent zirconyl chloride[ZrOCl2.l-l O] in 100 ml. of deionized'water, (b) when the initial pH ofthe resultant solution is less than 1, heating the solution or addingthereto NaOH until the pH is about 1.4-2, or alternatively, if the pH isgreater than 1 the pH is lowered to lor' less with a univalent acid,such as HCl, and (c) either heating or adding NaOH until the pH is aboutl .42;

11. The red-brown wetting solution of Example V-A which is obtained by(a) dissolving 1 weight percent of vanadium oxychloride [VOCl] in 100ml.of hot or boiling concentrated univalent acid such as HNO (b) raisingthe pH of the resultant solution to about 1.5-2 with a univalent alkalisolution and (c) heating the solution and adding a small amount of H 0thereto;

12. The red-brown colloidal wetting solution of Example V-B which isobtained by (a) dissolving 1 weight percent-of sodium vanadate [NaVOpotassium vanadate [KVO or ammonium meta-vanadate [NH VO in 100 ml. ofdeionized water and (b) lowering the initial alkaline pH of the solutionto a value of about 5-6 with HCl;

13. The brown-red colloidal wetting solution of Example V-C which isobtained by (a) adding 1/2 weight percent of vanadium tetrachloride [VClto concentrated HCl and (b) slowly raising thepH to about 1, e.g., bydiluting with H O;

14. The wetting solution of Example VI which is obtained'by (a)dissolving l/2 weight percent of green chromic chloride [CrCl .6H O],but probably more properly [Cr(H O) Cl ]Cl.2H O or [Cr(H O) Cl).6- H O]in 100 ml. of deionized water and (b) raising the initial pH of theresultant solution to about 5 with a univalent alkali;

15. The slightly yellow wetting solution of Example V" which is obtainedby (a) dissolving 1 weight percent of sodium molybdate [Na MoO.,.2H O orNa.,(- 6Mo O- ).4H O] in 100 ml. of deionized water and (b) lowering theinitial pH with a HCl to just below 7;

16. The faint yellow wetting solution of Example Vlll which is obtainedby (a) dissolving l-5 weight percent of sodium tungstate dihydrate [NaWO .2H O] in 100 ml. of deionized water and (b) lowering the pH with aHCl to below 1;

17. The muddy brown wetting solution of Example lX-B which is obtainedby (a) dissolving 1 weight percent of manganese trichloride [MnCl insufficient 18. The tan wetting solution of Example X-A which is obtainedby dissolving 1 weight percent of ferric chloride [FeCl .6H O] in 100ml. of deionized water, the dissolution being added by gradually heatingto about 50-80C and stirring to obtain a wetting solution at a pH of1.7-1.9;

19. The wetting solution of Example X-B which is obtained by (a)dissolving 0.5-5 weight percent of ferric chloride [FeCl .6l-l O] in 100ml. of deionized water, (b) adusting the final pH of the resultantsolution to about 1.5-2.0 with either HCl (at low ferric chlorideconcentrations) or NaOH (at high ferric chloride concentrations) and (c)heating the solution to 70C within 20 minutes;

20. The wetting solution of Example X-C which is obtained by (a)dispersing 1.5 weight percent of ferric chloride [FeCl .6H O] in 100 ml.of deionized water to a final pH of about 1.7-1.9 and (b) allowing theresultant solution to stand in ambient for 1-2 weeks;

21. The wetting solution of Example X-D which is obtained in the samemanner as Examples X-B and X-C, described above [(19) and (20)], exceptthat ferric bromide [FeBr or FeBr .6l-l O] is employed;

22. The wetting solution of Example X-E which is obtained by dissolving0.5-5 weight percent of ferric chloride [FeCl .6l-l O] in 100 ml. ofdeionized water which was first heated to 70C;

23..The wetting solution of Example X-F which is obtained by (a) addingl weight percent of ferric oxide [Fe O which was particulated andpowdered to a particulate size of about 150A in 100 ml. of deionizedwater, (b) ultrasonically agitating the mixture to aid in thedissolution of the ferric oxide and (c) lowering the pH of the resultantsolution from 3-3.5 to 1.0 with HCl;

24. The wetting solution of Example X-G which is obtained by (a) adding1 weight percent of ferric oxide [Fe O which was particulated andpowdered to a particulate size of about 150A in 100 ml. of deionizedwater, (b) ultrasonically agitating the mixture toaid in the dissolutionof the ferric oxide [Fe O and (c) lowering the pH of the resultantsolution from 3-35 to 1.0 with HCl;

25. The wetting solution of Example X-H which is obtained by (a) heating100 ml. of deionized water to 80C and (b) adding 1-2 weight percentofferric chloride [FeCl .6H O] to the deionized water with stirringuntil dissolution occurs;

26. The blue wetting solution of Example Xl-A which is obtained by (a)dissolving 1 weight percent of cobaltous chloride [CoCl .6H O] in 100ml. of deionized water and (b) raising the pH from 4.9-5.1 to about7.0-7.2 with lN-NaOH;

27. The wetting solution of Example Xl-B which is obtained by (a) adding1 weight percent of cobaltous chloride [CoCl .6H O] to 100 ml. ofdeionized water, (b) adding sufficient NaOH to the resultant solution toeffect the onset of a Tyndal cone and (c) heating the solution to about60-70C for 2 days while adusting the pH, as necessary, with NaOH toabout 4',

28. The wetting solution of Example Xl-C which is obtained by (a) adding1 weight percent of cobaltous chloride [CoCl .6H O] to 100 ml. ofdeionized water, (b) heating the resultant solution to about 60-70C withconstant stirring, (0) raising the pH to about 2 with NaOH, (d) heatingthe solution again and raising the pH again to about 2 and (e)continuing the above procedure until the onset of a Tyndal cone or forabout 6 hours (the resultant wetting solution has a life of about onehour);

29. The green wetting solution of Example XII-A which is obtained by (a)dissolving one weight percent of nickel chloride [NiCl .6H O] in 100 ml.of deionized water, (b) adding sufficient NaOH to effect the onset of aTyndal cone and (c) heating the solution at about 6070C for 2 dayskeeping the pH adjusted to about 4 with NaOH;

30. The pale green wetting solution of Example Xll-B which is obtainedby (a) dissolving 1 weight percent of nickel chloride [N iCl .6H O] indeionized water and (b) raising the pH of the resultant solution toabout 6-6 .5 with Na0H;

31. The blue wetting solution of Example XV which is obtained by (a)dissolving 1 weight percent of cupric chloride [CuCl in 100 ml. ofdeionized water and (b) heating the resultant solution to about C whilecontinually adjusting the pH to about 6 with Na0H;

32. The wetting solution of Example XVIII which is obtained by (a)dissolving 1 weight percent of zinc chloride [ZnCl in ml. of deionizedwater, (b) adding a sufficient amount of a univalent alkali, such asNaOH, to effect a slight precipitate at a pH of about 4, (c) heating theresultant solution at 60-80C until the precipitate dissolves, (d) addingdilute univalent alkali, such as NaOH, until the onset of a Tyndal cone,and tinally, (e) the heating and acid addition steps are repeated untila colloidal solution results;

33. The wetting solution of Example XIX which is obtained by (a)dissolving 1 weight percent of cadmium chloride [CDCL L /zH O] in 100ml. of deionized water and (b) slowly raising the pH of the resultantsolution (over several hours time) to about 8-9 with a very diluteunivalent alkali, such as NaOH,

during which time the solution is slightly (about 34. The yellow wetting amioh' of Example XX which is obtained by (a) dissolving 1 weightpercent of mercuric chloride (corrosive sublimate) [HgCl in 100 ml. ofdeionized water and (b) slowly adding a dilute univalent alkali, such asNa0H, to raise the pH to about 5;

35. The wetting solution of Example XXI-A which is obtained byv (a)adding 1 weight percent of finely powdered aluminum chloride [AlCl to100ml. of deionized water, (b) raising the pH to about 5.2 with aunivalent alkali such as NaOH and (c) heating the resultant solution forabout 2 hours at about 60-80C;

36. The wetting solution of Example XXI-B which is obtained by (a)heating 100 m1. of deionized water to about 60C. (b) adding 1 weightpercent of aluminum chloride [AlCl .H O] thereto and (0) while thesolution is still hot raising the pH from 2.5 to about 5.0- 5.2 with aunivalent alkali, such as lN-NaOH;

37. The wetting solution of Example XXII-A which is obtained by (a)dissolving 1 weight percent of indium trichloride [lnCl in 100 ml. ofdeionized water and (b) raising the pH of the resultant solution toabout 3 with NaOH;

38. The whitish wetting solution of Example XXII-B which is obtained by(a) dissolving )2 weight percent of indium monochloride [lnCl] in 100m1. of deionized water and (b) raising the pH to about 3.9 with dilute(factor of 20 with H 0) Nl-l llH;

39. The yellow wetting solution of Example XXlll which is obtained by(a) adding 0.1 weight percent of thallium monochloride [TlCl] to 100 ml.of deionized water, (b) raising the pH of the resultant solution toabout 7.58 with NaOH and adding a few ml. of dilute potassiumferricyanide [K Fe(CN) to the solution with stirring; I

40. The wetting solution of Example XXIV which is obtained by (a) adding0. lweight percent of silicon tetrachloride or tetrachlorosilane [SiClto concentrated HCl and (b) stirring the resultant solution;

41. The colloidal wetting solution of Example XXV which is obtained by(a) adding 1-2 weight percent of germanium tetrachloride [GeCl toconcentrated HCl and (b) diluting the resultant solution with H 0 toraise the pH to about 0.5;

42. The wetting solution of ExampleXXVl-A which is obtained by (a)dissolving l-3 weight percent of stannic chloride [SnCl .5H O] in 100ml. of deionized water and (b) permitting the resultant solution tostand at room temperature for l-3 days or at an elevated temperature(about 60C) for about 1 hour until a flocculate forms. The supernatantportion is a wetting solution;

43. The wetting solution of Example XXVl-B which is obtained by (a)dissolving kweight percent of stannic chloride [SnCl .5H O] in .100 ml,of deionized water and (b) permitting the solution of stand for about 1month until the pH thereof is about 0.8 l.8 and a flocculate forms atthe bottom thereof. The supernatant portion of this solution is thewetting solution;

44. The colorless wetting solution of Example XXVI- C which is obtainedby adding sufficient HCl to the bottom layer (containing the flocculate)of the solution of Example XXVI-B, described above, to lower the pH toabout 0.8-].8;

45. The colorless wetting solution of Example XXVI- D which is obtainedby heating to 90C for about 30 minutes the bottom layer (containing theflocculate) of the solution of Example XXVI-B, described above;

46. The wetting solution of Example XXVI-E which is obtained by (a)dissolving 1 weight percent of sodium hydroxo stannate [Na Sn0 .3H 0 orNa Sn(0H) in 100 ml. of deionized water and (b) lowering the pH of theresultant solution to about 7.5-8.5 by the slow addition of HCl;

47. The colorless (milky white) wetting solution of Example XXVlll whichis obtained by (a) dissolving l weight percent of bismuth trichloride[BiCl in 100 ml. of dilute (pH about 0.2) HCl and (b) raising the I pHof the resultant solution to about 3-4 with NaOH;

suitable colloidal solution with which it is destined to be combined.Following the pH adjustment, if required, the aqueous AgNO solution isadded to a selected suitable colloidal solution comprising a halide ionand insoluble colloidal hydrous oxide particles of a particular element.Upon the addition of the aqueous AgNO solution, a reaction occursbetween the Agfions and the halide ion, e.g., Cl, Br, 1, contained inthe colloidal solution whereby a silver halide, e.g., AgCl, AgBr, Agl,forms and is precipitated or deposited or sorbed on the individualcolloidal hydrous oxide particles.

It is to be noted and stressed at this point that both the silver halideformed and the solution containing the silver halide are wetting, i.e.,they both are capable of rendering a hydrophobic surface hydrophilic andalso the silver halide composition formed is capable of adhering verywell to the hydrophobic surface. In this regard, a film of the silverhalide deposited on a hydrophobic surface, e.g.,polytetrafluoroethylene, cannot be removed by the application of acellophane adhesive tape peel test thereto. It is also to be noted andstressed at this point that usually upon the addition of an electrolyteto a colloidal solution flocculation of the colloid occurs destroyingthe colloidal solution and the properties associated therewith, e.g.,wetting ability. Surprisingly, such has been found not to occur with theaddition of the silver salt, e.g., AgN0 to the abovedescribed colloidalwetting solutions. The resultant solution retains both its colloidalstate and its wetting ability (along with the formed silver halide).

Where the resultant silver halide composition is intended forphotographic applications, a suitable support base, e.g., a cellulosesupport, a paper support, etc., is selected. Suitable support bases andthe properties thereof depend upon the purpose of the photographicapplication. Such support bases are well known in the art to thoseskilled therein and will not be elaborated herein. The selected supportbase (hydrophilic or hydrophobic) is immersed in the resultant colloidalsolution, comprising colloidal hydrous oxide particles having a silverhalide deposit thereon, for a period of time sufficient to uniformly wetthe surfaces thereof with the solution and deposit a uniform film ofsilver halide coated colloidal particles thereon. For most support basesan immersion of about one minute at 25C is sufficient. In the case of aTeflon (polytetrafluoroethylene) support base, which is very hydrophobicand upon which a silver halide gelatin film cannot adequately adhere, animmersion of about 10 minutes is required.

It is to be noted that the amount of deposited film can be controlled bythe length of time the surface or support base is immersed in theresultant wetting silver halide colloidal solution. The deposit can alsobe built up by removing the support base from the colloidal solution,rinsing, drying, heating at 60 to C for l-5 minutes and then repeatingthe sequence of steps starting with the immersion.

The support base is removed from the wetting silver halide containingcolloidal solution, is rinsed in flowing deionized water and is then airdried. A surface coated with a wetting silver halide film is thenselectively exposed to a source of suitable photographic light radiationto obtain a latent image comprising silver metal [Ag] nuclei on thoseareas of the surface exposed. It is to be noted that the silver halidefilm coated surface is exposed to the light radiation for a period oftime sufficient to form the latent image. Such a period of time isreadily ascertained experimentally by one skilled in the art for aparticular light source. It is to be noted, however, that the time ofexposure is interdependent upon the intensity of the light source, i.e.,upon the amount of energy transmitted by the source to the surface. Thisinterdependency is well known in the art or is easily ascertained by oneskilled therein. A typical exposure may range from 1 to 10millijoules/cm at a wavelength ranging from 2000 to 3600A. It is to bepointed out that the wavelength dependence can be altered employingstandard techniques well known in the art, e.g., by the use of variousdyes.

The latent image is then developed using conventional silver halidephotographic developers, including development of the silver halide byexposure to suitable radiation, which are well known to those skilled inthe art and which will not be elaborated herein. Alternatively, thelatent image can be physically developed by immersion in an electrolessmetal plating solution wherein the silver nuclei catalyze the reductionof electroless metal ions of electroless metal to obtain an electrolessmetal pattern corresponding to the latent image.

EXAMPLE I A. A 1.0 weight percent aqueous AgNO solution was prepared.The pH of the solution was adjusted with HNO to a value of about 5. Theresultant AgNO solution was then added, in a concentration of 005 Weightpercent of the total solution, to a stable colloidal solution comprising(1) colloidal particles of a hydrous oxide of beryllium and (2) chlorideions, to form silver chloride which was deposited on or covered each ofthe individual colloidal beryllium hydrous oxide particles. Thecolloidal solution was prepared in the following manner. One weightpercent of beryllium chloride [BeCl was added to and dissolved in 100ml. of deionized water. The initial pH was raised with NaOH until it wasabout 5 whereat a Tyndal cone was observed.

A hydrophobic polyethylene terephthalate film, commercially obtained,was immersed in the resultant wetting silver chloride depositedcolloidal solution for about 2 seconds at 25C. The film was removed andrinsed in flowing deionized water for one minute whereafter it was airdried. This procedure was then repeated but with a hydrophobic polyimidefilm, commerically obtained. This procedure was repeated again but witha hydrophobic polytetrafiuorethylene film which was immersed in theresultant solution for 20 minutes. i

A surface of each of the dried films (polyethylene terephthalate,polyimide and polytetrafluoroethylene), having a photosensitive layercomprising silver chloride deposited or coated colloidal berylliumhydrous oxide particles, was then selectively exposed to a source ofultraviolet radiation (l millijoules/cm intensity, A 2537A). Thelight-exposed surface was then immersed in an electroless copper platingsolution, commercially obtained. to obtain a 0.01 mil thick electrolesscopper deposit on the areas of each surface exposed to the light.

B. The procedure of Example l-A was repeated except that 0.5 weightpercent (of the total weight of the resultant mixture) of AgNO was addedto the colloid solution.

A physical development comprising a 0.01 mil thick electroless copperpattern on each of the three respective film surfaces was obtained.

C. The procedure of Example I-A was repeated except that the berylliumhydrous oxide colloid particle containing solution was prepared in thefollowing manner. One weight percent of beryllium chloride [BeCl' wasdissolved in 100 ml. of deionized water. The initial pH of the solutionwas raised with NaOH until it was about 5 whereat a Tyndal cone wasobserved. A colorless (e.g., light, milky white) wetting solution wasobtained. The pH of the aqueous AgNO solution was adjusted to about 5and was combined with the colloidal solution in a concentration of 0.05weight percent Ag- N0 A physical development comprising a 0.01 mil thickelectroless copper pattern on each of the three respective film surfaceswas obtained.

D. The procedure of Example l-A was repeated except that the berylliumhydrous oxide colloid particle containing solution was prepared in thefollowing manner. About 1/4 weight percent of beryllium chloride [BeClwas added to deionized water. The resultant solution was heated forabout l hour at 70"C resulting in a colorless (light, milky white)colloid wetting solution. The aqueous AgNO solution was adjusted to a pHof 5.0 prior to the addition thereof to the colloidal solution.

A physical development comprising a 0.01 mil thick electroless copperpattern on each of the three respective film surfaces was obtained.

EXAMPLE II The procedure of Example I-A was repeated except that acolloid solution comprising. colloidal hydrous o'xide particles ofmagnesium was employed. The colloidal solution was prepared in thefollowing manner. One weight percent of magnesium chloride [MgCl or MgCl.2H O] was dissolved in ml. of deionized water. The initial pH of thesolution was then raised with a univalent alkali, i.e. NaOH to about 8.A colorless (light, milky white) wetting solution was produced. Theaqueous AgNO solution was added to the colloidal solution.

A physical development comprising a 0.01 mil thick electroless copperpattern on each of the three respective film surfaces was obtained.

EXAMPLE 111 A. The procedure of Example l-A was repeated except that a 1weight percent aqueous AgNO solution was prepared and added to acolloidal solution comprising colloidal hydrous oxide particles ofchromium. The AgNO was present in the resultant solution in aconcentration of 0.5 weight percent. The colloidal solution was preparedin the following manner. One-half weight percent of a green chromicchloride [CrCl .6l-1 O] was dissolved in 100 ml. of deionized water. Theinitial pH was raised to about 5 with NaOH to obtain a green wettingsolution. Prior to combining the aqueous solutions, the pH of the AgNOsolution was adjusted to about 5 with HNO A physical developmentevidenced by a 0.01 mil thick electroless copper pattern on each of thethree respective film surfaces was obtained.

B. The procedure of Example Ill-A was repeated except that the AgNOadded to the colloidal solution was present in an amount of 0.01 weightpercent. The results obtained were the same as in Example II-A above.

EXAMPLE IV The procedure of Example l-A was repeated except that a 0.1weight percent aqueous AgNO solution was prepared. The aqueous AgNOsolution was combined with a stable aqueous colloidal solutioncomprising colloidal hydrous oxide particles of cobalt, The AgNO beingpresent in a concentration of 0.01 weight percent. The colloidalsolution was prepared in the following manner. One weight percent ofcobaltous chloride [CoCl .6H O] was added to 100 ml. of deionized water5 to form a rose colored solution having a' pH of about 4.9-5.1. The pHwas then raised with NH OH to about 7.5-7.8 to obtain a blue wettingsolution.

A physical development evidenced by a 0.01 mil thick electroless copperpattern on each of the. three respective film surfaces was obtained.

EXAMPLE V The procedure of Example l-A was repeated except that the 0.1weight percent aqueous AgNO solution was combined with a stablecolloidal solution comprising colloidal hydrous oxide particles ofcopper, the

AgNO being present therein in a concentration of 0.05 weight percent.The colloidal solution was prepared in the following manner. One weightpercent of cupric chloride [CuCl was dissolved in 100 ml. of deionizedwater. The pH of the solution was raised by the slow addition of a 10%solution of NH OH to a pH of 7.2-7.5. This was a wetting solution.

A physical development evidenced by a 0.01 mil thick electroless copperpattern on each of the three respective film surfaces was obtained.

EXAMPLE VI A. The procedure of Example l-A was repeated except that a0.1 weight percent aqueous AgNO solution was prepared. The resultantAgNo solution was then combined with a colloidal aqueous solutioncomprising insoluble hydrous oxide particles of zinc, the AgNO beingpresent in the resultant mixture in a concentration of 0.05 weightpercent. The colloidal hydrous zinc oxide solution was prepared in thefollowing manner. One weight percent of zinc chloride -[ZnCl wasdissolved in 100 ml. of deionized water. A sufficient amount of NH OHwas then added to the resultant solution to obtain a pH of about 7.0-7.5to yield a colloidal wetting solution.

A physical development evidenced by a 0.01 mil thick electroless copperpattern on each of the three respective film surfaces was obtained.

B. The procedure of Example Vl-A was repeated except that the AgNO wasadded to the colloidal solution in a concentration of 0.05 weightpercent. The results obtained were the same as in Example Vl-A.

EXAMPLE Vll A. The procedure of Example l-A was repeated except that a0.01 weight percent aqueous AgNO solution was prepared whose pH wasadjusted to about 5.2 by the addition of HNO thereto. The resultant AgNOsolution was then combined with a colloidal aqueous solution comprisinginsoluble hydrous oxide particles of aluminum. The AgNO was present inthe resultant mixture in a concentration of 0.5 weight percent. Thecolloidal solution was prepared in the following manner. One weightpercent of finely powered aluminum chloride [AlCl was added to 100 ml.of deionized water. The pH of the resultant solution was raised withNaOH to about 5.2. This solution was heated for about 2 hours at about6080C to yield a colorless (milky white wetting solution.

A physical development evidenced by a 0.01 mil thick electroless copperpattern on each of the three respecitve film surfaces was obtained.

B. The procedure of Example VII-A was repeated except that the AgNO wasadded to the colloidal solution in a concentration of 0.05 weightpercent. The results obtained were the same as in Example Vll-A.

EXAMPLE \llllv The procedure of Example l-A was repeated except that a0.1 weight percent aqueous AgNO solution was prepared whose pH wasadjusted to about 3 by the addition of HNO thereto. The resultant AgNOsolution was then combined with a colloidal aqueous solution comprisinginsoluble hydrous oxide particles of indium, the AgNO being present inthe resultant mixture in a concentration of 0.05 weight percent. Thecolloidal solution was prepared in the following manner. One weightpercent of indium trichloride [lnCl was dissolved in ml. of deionizedwater. The pH of this solution was raised to about 3 with NaOH yieldinga colorless (milky white) wetting solution.

A physical development evidenced by a 0.0l mil thick electroless copperpattern on each of the three respective film surfaces was obtained.

EXAMPLE IX A. The procedure of Example I-A was repeated except that a0.01 weight percent aqueous AgNO solution was prepared whose pH wasadjusted to about 1.0 by the addition of HNO thereto. The resultant AgNOsolution was then combined with a colloidal aqueous solution comprisinginsoluble hydrous oxide particles of tin, the AgNO being present in theresultant mixture in a concentration of 0.05 weight percent. Thecolloidal solution was prepared in the following manner. One weightprecent of stannic chloride [SnCl.,.5H O] was dissolved in 100 ml. ofdeionized water. The solution was allowed to stand at a temperature ofabout 60C for 1 hour until a flocculate formed.

A physical development evidenced by a 0.01 mil thick electroless copperpattern on each of the three respective film surfaces was obtained.

B. The procedure of Example lX-A was repeated except that the colloidalsolution was prepared in the following manner. One-half weight precentof stannic chloride [SnCl.,.5H O] was dissolved in 100 ml. of deionizedwater. The resultant solution was allowed to stand for approximately 1month until the pH thereof was about 0.8-1.8 and a flocculate formed atthe bottom thereof. The supernatant portion is a wetting solution. ThepH of the AgNO was adjusted to about 0.8-1.8 by the addition of HNOthereto and was then combined with the supernatant portion.

A physical development evidenced by a 0.01 mil thick electroless copperpattern on each of the three respective film was obtained.

C. The procedure of Example lX-A was repeated except that the colloidalwetting solution was prepared in the following manner. The bottom layercontaining the flocculate, described in Example lX-B, above, had addedthereto sufficient HCl to lower the pH to about 0.8 -1 .8 to yield acolorless (milky white) wetting solution. The results achieved were thesame as in Example lX-B, above.

D. The procedure of Example lX-B was repeated except that the colloidalwetting solution was prepared in the following manner. The bottom layercontaining the flocculate of the solution of Example IX-B, describedabove, was heated to 3090C for about 30 minutes to yield a colorless(milky white) wetting solution. The results obtained were the same as inExample lX-B, above. 1

E. The procedure of Example lX-A was repeated except that the colloidalwetting solution was obtained in the following manner. To concentratedHCl was added 2 weight percent of stannic chloride [SnCl .5H O]. Theinitial pH of this solution was raised to within the range of 0.5-0.8with NaOH to yield a colloidal wetting solution. The pH of the aqueousAgNO solution was similary adjusted to 0.5-0.8 by the addition theretoof HNO prior to the combining with the colloidal solution.

A physical development evidenced by a 0.01 mil thick electroless copperpattern on each of the three respective film surfaces was obtained.

F. The procedure of Example lX-A was repeated except that the colloidalwetting solution was prepared in the following manner. To concentratedHBr was added l-2 weight percent of stannic bromide [SnBr The pH of theresultant solution was then raised to within the range of 1.0-1.1 withNaOH. The pH of the aqueous AgNO solution was then lowered to 1.0-1.1 bythe addition of HNO thereto prior to combining with the col loidalsolution. Upon the combining of the AgNO solution with the colloidalwetting solution a silver bromide, deposit on the colloidal tin hydrousoxide partcles was obtained which was photosensitive.

A physical development evidenced by a 0.01 mil thick electroless copperpattern on each of the three respective film surfaces was obtained.

EXAMPLE 'X A. The procedure of Example l-A was repeated except that a0.1 weight percent aqueous AgNO solution was prepared whose pH wasadjusted to about 1.7-1 .9 by the addition of HNO thereto. The resultantAgNO solution was then combined with a colloidal aqueous solutioncomprising insoluble hydrous oxide particles of iron, the AgNO beingpresent in the resultant mixture in a concentration of 0.05 weightpercent. The colloidal solution was prepared in the following manner.One weight percent of ferric chloride [FeCl .6H O] was dissolved in 100ml. of deionized water. This solution was aided by gradually heating toabout 60-80C and stirring. At a pH of about 1.7-1 .9 a tan wettingsolution was produced.

A physical development evidenced by a 0.01-mil thick electroless copperpattern on each of the three respective film surfaces was obtained.

B. The procedure of Example X-A was repeated except that the colloidalwetting solution was prepared in the followingmanner. One-half weightpercent of ferric chloride [FeCl .6H O] was dissolved in 100 ml. ofdeionized water. The final pH of this solution was ad justed to about1.5-2.0 with HCl. The solution was then heated to 70C within 20 minutesyielding a coffeepumpkin color wetting solution.

A physical development evidenced by a 0.01 mil thick electroless copperpattern on each of the three respective film surfaces was obtained.

C. The procedure of Example X-A was repeated except that the colloidalwetting solution was prepared in the following manner. One-half weightpercent of ferric 14} chloride [FeCl .6H O] was dispersed in 100 ml. ofdeionized water of a final pH of about 1.7-1 .9. The solution wasallowed to stand in ambient for l-2 weeks thereby yielding acoffee-pumpkin color wetting solution. Prior to the combining of theAgNO with the resultant wetting solution the aqueous AgNO solution wasadjusted to a pH of l.7-l'.9 by the addition of HNO thereto.

A physical development evidenced by a 0.01 mil thick electroless copperpattern on each of the three respective film surfaces was obtained.

D. The procedure of Example X-A was repeated except that the colloidalwetting solution was prepared in the following manner. 100 ml. ofdeionized water was first heated to C. 1.5-5 weight percent of ferricchloride was added thereto and dissolved therein. The final pH of thiswetting solution was 1.5-2.0. The pH of the aqueous AgNO; solution wasadjusted to 1.5-2.0 by the addition of HNO thereto prior to combiningthe AgNO with the colloidal solution.

A physical development evidenced by a 0.01 mil thick electroless copperpattern on each of the three respective film surfaces was obtained.

E. The procedure of Example X-A was repeated except that the colloidalwetting solution was prepared in the following manner. 100 ml. ofdeionized water was heated to C. l-2 weight percent of ferric chloridewas added and the solution was stirred until the ferric chloridedissolved. Upon cooling to 25C a vermouth colored wetting solution wasobtained. The pH of the aqueous AgNO solution was adjusted to 1.3 by theaddition of HNO thereto and then combined with the resultant wettingsolution.

A physical development evidenced by a 0.01 mil thick electroless copperpattern on each of the three respective film surfaces was obtained.

F. The procedure of Example X-A was repeated except that 0.5 weightpercent of sodium bromide (NaBr) was added to the colloidal wettingsolution prior to the combination of AgNO therewith. A mixed silverhalide salt was obtained, namely, silver bromide and silver chloride,which were deposited on the hydrous oxide colloidal particles to form aphotosensitive composition.

G. The procedure of Example X-F was repeated except that 0.5 weightpercent of sodium iodide (Nal) was added. A mixed silver chloride,silver iodide deposit was obtained to yield a photosensitivecomposition.

H. The procedure of Example X-A was repeated except that the colloidalwetting solution was prepared as follows. One weight percent of ferricbromide [FeBr .6H O] was dissolved in ml. of deionized water. Thesolution was heated to about 60C forabout 16 hours resulting in acolloidal wetting solution having a pH of about 1.8. The aqueous AgNOsolution was adjusted to a pH of 1.8 by the addition of HNO thereto andwas then combined with the colloidal solution. Silver bromide wasdeposited or precipitated on the colloidal iron hydrous oxide particlesto form a photosensitive composition.

A physical development evidenced by a 0.01 mil thick electroless copperpattern on each of the three respective film surfaces was obtained.

1. The procedure of Example X-H was repeated except that 2.0 weightpercent of ferrous iodide [Fel .4- H O] was employed. The pH of theresultant colloidal wetting solution was 2.5. The pH of the aqueous AgNOsolution was adjusted to about 2.5 by the addition of HNO thereto andwas then added to the colloidal wetting solution. Silver iodide wasdeposited or precipitated on the colloidal iron hydrous oxide particlesto form a photosensitive composition.

A physical development evidenced by a 0.01 mil thick electroless copperpattern on each of the three respective film surfaces was obtained.

It is to be understood that the above-described embodiments are simplyillustrative of the principles of the invention. Various othermodifications and changes may be made by those skilled in the art whichwill embody the principles of the invention and fall within the spiritand scope thereof.

What is claimed is:

1. A photosensitive silver halide composition comprising a silver halidedeposited on colloidal particles of a hydrous oxide of an elementselected from the group consisting of Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn,Fe, Co, Ni, Cu, Zn, Cd, Hg, Al, in, T1, Si, Ge, Sn, Bi, Th, and mixturesthereof.

2. The composition as defined in claim 1 wherein said silver halidecomprises silver chloride.

3. A photosensitive silver halide composition comprising silver halideprecipitated in the presence of a stable aqueous colloidal wettingsolution, formed by a hydrolysis and nucleation reaction, comprisinginsoluble hydrous oxide particles of an element selected from the groupconsisting of Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Cd,Hg, Al, ln, Tl, Si, Ge, Sn, Bi, Th, and mixtures thereof, said particleshaving a size within the range of A to l0,000A and said hydrolysisreaction including at least (1) dissolution of a salt of said selectedelement in an aqueous medium and (2) maintenance of the pH of saidaqueous medium at a point where no flocculate results.

4. The composition as defined in claim 3 wherein said silver halidecomprises silver chloride.

5. A method of forming a wetting photosensitive silver halidecomposition which comprises combining a suitable silver salt with astable aqueous colloidal wetting solution, formed by a hydrolysis andnucleation reaction, comprising (a) a halide ion and (b) insolublehydrous oxide particles of an element selected from the group consistingof Be,Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg, A], In,Tl, Si, Ge, Sn, Bi,

further comprises treating the exposed film with a Th, and mixturesthereof, said particles having a sizewithin the range of 10A to 10,000Aand said hydrolysis reaction including at least (1) dissolution of asalt of said selected element in an aqueous medium and (2) maintenanceof the pH of said aqueous medium at a point where no flocculate results.

6. The method as defined in claim 5 wherein said suitable silver saltcomprises AgNO and said halide ion comprises a chloride ion.

7. A method of rendering a surface photosensitive which comprises: I

a. combining a water-soluble silver species with a stable aqueouscolloidal wetting solution, formed by a hydrolysis and nucleationreaction, comprising a halide species and insoluble hydrous oxideparticles of an element selected from the group consisting of Be, Mg,Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg, A], In, Tl, Si,Ge, Sn, Bi, Th, and mixtures thereof, to precipitate a silver halide andto coat said hydrous oxide particles with said precipitated silverhalide; and

b. contacting the surface with said coated particles to deposit aphotosensitive film thereof thereon.

8 The method as defined in claim 7 wherein said silver species comprisesAgNO and said halide species comprises chloride ions.

9. In the method of making a photographic image comprising exposing to alight image a photosensitive film comprising silver halide to form alatent image therein, the improvement wherein the photosensitive filmwhich comprises a silver halide deposited on insoluble collidalparticles of a hy-' drous oxide of an element selected from the groupconsisting of Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Cd,Hg, Al, In, Tl, Si, Ge, Sn, Bi, Th, and mixtures thereof. 1( The methodas defined in claim 9 wherein said silver halide comprises silverchloride.

11. The method as defined in claim 9 which suitable developer to developa visible image therein.

12. The method as defined in claim 9 which further comprises depositingsaid silver halide deposited colloidal particles on a support medium toform the photosensitive film thereon.

L SSS-PT UNITED STATES PATENT OFFICE CERTIFICATE OF CQRRECTIQN p 3, 5,95 Damd December 17, 197A lnventor(s) J- 1" Ken-ney It is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

In the specification, Column 1, line ll, "2. 1 Description" should read2. Description-. Column 2, line 27, "hd Th" should read --ahd Th-, line31, "halid" should read -halide-; line 65, "Vol. ll," should read -Vol.II,-. Column 3, line 1, "nd Sons should read -and Sons; lin 33, M to to"should read --to--; line 55, "water 1" should read water until l-; line59, "example" should read -EXample. Column A, line 13, "0.5-5" shouldread -O.5l.5-5 line 65, "0.6-8" shouldread --o.6-o.8--. Column 6, line32, "CDCL .l/2H2O" should read -CdCl2.l/2H2O- line 53, "60C." shouldread -60C,--. Column 7, line 2i, "1/2 weight" should read --l/2-2weight--; line 26, "of stand" shoid read --to stande-.

Column 9, line 1%, "ions of" should read --ions to--. Column ll, line 1,"cobalt, The" should read --cobalt, the, line 33, AgNog" should read--AgNO line 37, '0.05" should read -O.5-5 line 5M, "0.01" should read-O.l-; line 62, "powered" should read --powdered--. Column 12, line #6,"precent" should read --percent-; line 57, "film was" should read --filmsurfaces was-. Column 1M, line 2, "water of" should read water to--.

In the claims, Column 16, claim 9, line 31, "wherein" should read-wherein:-.

Signed and Eaealcd this twenty-sixth Day Of August 1975 [SEAL] A ttesr.-

RUTl-l C. MASON C. MARSHALL DANN Arresting Officer Commissioner ofPatents and Trademarks Q L-566-PT UNITED STATES PATENT OFFICE L. JIFICATE OF CORRECTION Patent 3,85%,952 Dated December 17, 1974Inventor-(s) Kenney h is certified that error appears in theabove-idenrified parent and that said Letters Parent are herebycorrected as shown below:

In the specification, Column 1, line ll, 2 1 Description" should read 2.Description. Column 2,

' line 27, "nd Th should read and Th"; line 31, halid" should readhalide-, line 65, "vol. ll, should read Vol. II,--. Column 3, line l,"nd Sons should read and Sons"; line 33, to to" should read -to--; line55, "water 1" should read Water until l-, line 59, "example" should read-EXample. Column L, line 13,

9 "0.5-5" should read "0.5-1.5"; line 65, 0.6-8 should read --o.6-o.8--.Column 6, line 32, CDCL .l/2H O" should read -CdCl2.l/2H O--- lin 53,"60C." should read --60C,--. Column 7, line 2i, "1/2 Weight should read-l/22 weight"; line 26, "of stand" should read to 6 stand\--.

Column 9, line l t, "ions of" should read ions to. Column ll, line 1,"cobalt, The" should read cobalt, the, line 33, AgNog" should read--Agl\TO --5 line 37, 0.05 should read --o.5--, lihs 5A, "0.01" shouldread O.l-; line 62, "powered" should read powdered-- Column 12, line #6,"precent" should read -percent-; line 57, film was" should read filmsurfaces was--. Column l t, line 2, water of" should read water to.

In the claims, column 16, claim 9, line 31, wherein should read Wherein:

Signed and Sealed this twenty-sixth Day Of August1975 Q [SEAL] Arrest:

RUTH C. MASON c. MARSHALL DANN Commissioner of Patentr and TrademarksAlresting Officer

1. A PHOTOSENSITIVE SILVER HALIDE COMPOSITION COMPRISING A SILVER HALIDEDEPOSITED ON COLLOIDAL PARTICLES OF A HYDROUS OXIDE OF AN ELEMENTSELECTED FROM THE GROUP CONSISTING OF BE, MG, TI, ZR, V, CR, MO, W, MN,FE, CO, NI, CU, ZN, CD, HG, AL, IN, TL, SI, GE, SN, BI, TH, AND MIXTURESTHEREOF.
 2. The composition as defined in claim 1 wherein said silverhalide comprises silver chloride.
 3. A photosensitive silver halidecomposition comprising silver halide precipitated in the presence of astable aqueous colloidal wetting solution, formed by a hydrolysis andnucleation reaction, comprising insoluble hydrous oxide particles of anelement selected from the group consisting of Be, Mg, Ti, Zr, V, Cr, Mo,W, Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg, Al, In, Tl, Si, Ge, Sn, Bi, Th, andmixtures thereof, said particles having a size within the range of 10Ato 10,000A and said hydrolysis reaction including at least (1)dissolution of a salt of said selected element in an aqueous medium and(2) maintenance of the pH of said aqueous medium at a point where noflocculate rEsults.
 4. The composition as defined in claim 3 whereinsaid silver halide comprises silver chloride.
 5. A method of forming awetting photosensitive silver halide composition which comprisescombining a suitable silver salt with a stable aqueous colloidal wettingsolution, formed by a hydrolysis and nucleation reaction, comprising (a)a halide ion and (b) insoluble hydrous oxide particles of an elementselected from the group consisting of Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn,Fe, Co, Ni, Cu, Zn, Cd, Hg, Al, In, Tl, Si, Ge, Sn, Bi, Th, and mixturesthereof, said particles having a size within the range of 10A to 10,000Aand said hydrolysis reaction including at least (1) dissolution of asalt of said selected element in an aqueous medium and (2) maintenanceof the pH of said aqueous medium at a point where no flocculate results.6. The method as defined in claim 5 wherein said suitable silver saltcomprises AgNO3 and said halide ion comprises a chloride ion.
 7. Amethod of rendering a surface photosensitive which comprises: a.combining a water-soluble silver species with a stable aqueous colloidalwetting solution, formed by a hydrolysis and nucleation reaction,comprising a halide species and insoluble hydrous oxide particles of anelement selected from the group consisting of Be, Mg, Ti, Zr, V, Cr, Mo,W, Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg, Al, In, Tl, Si, Ge, Sn, Bi, Th, andmixtures thereof, to precipitate a silver halide and to coat saidhydrous oxide particles with said precipitated silver halide; and b.contacting the surface with said coated particles to deposit aphotosensitive film thereof thereon.
 8. The method as defined in claim 7wherein said silver species comprises AgNO3 and said halide speciescomprises chloride ions.
 9. In the method of making a photographic imagecomprising exposing to a light image a photosensitive film comprisingsilver halide to form a latent image therein, the improvement whereinthe photosensitive film which comprises a silver halide deposited oninsoluble collidal particles of a hydrous oxide of an element selectedfrom the group consisting of Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co,Ni, Cu, Zn, Cd, Hg, Al, In, Tl, Si, Ge, Sn, Bi, Th, and mixturesthereof.
 10. The method as defined in claim 9 wherein said silver halidecomprises silver chloride.
 11. The method as defined in claim 9 whichfurther comprises treating the exposed composition with a suitabledeveloper to develop a visible image therein.